para-Selective arylation and alkenylation of monosubstituted arenes using thianthrene S-oxide as a transient mediator

Xiao-Yue Chen; Xiao-Xue Nie; Yichen Wu; Peng Wang

doi:10.1039/d0cc00641f

Intermolecular Diastereoselective Annulation of Azaarenes into Fused N-heterocycles by Ru(II) Reductive Catalysis

10.21203/rs.3.rs-963422/v1 ◽

2021 ◽

Author(s):

He Zhao ◽

Yang Wu ◽

Chenggang Ci ◽

Zhenda Tan ◽

Jian Yang ◽

...

Keyword(s):

Building Block ◽

Transfer Rate ◽

Hydrogen Transfer ◽

Functional Group ◽

Critical Role ◽

Hydride Transfer ◽

Mechanistic Studies ◽

Mild Conditions ◽

Excellent Selectivity ◽

Coupling Sequence

Abstract Despite the important advances in azaaryl C−H activation/functionalization, reductive functionalization of ubiquitously distributed but weakly reactive azaarenes remains to date a challenge. Herein, by a strategy incorporating a tandem coupling sequence into the reduction of azaarenes, we present a dearomative annulation of azaarenes into promising fused syn-N-heterocycles by combination with a large variety of aniline derivatives and paraformaldehyde under ruthenium(II) reductive catalysis, proceeding with excellent selectivity, mild conditions, and broad substrate and functional group compatibility. Mechanistic studies reveal that the products are formed via hydride transfer-initiated β-aminomethylation and α-arylation of the pyridyl core in azaarenes, paraformaldehyde serves as both the C1-building block and reductant precursor, and the use of Mg(OMe)2 base plays a critical role in determining the reaction chemo-selectivity by lowering the hydrogen transfer rate. The present work opens a door to further develop valuable reductive functionalization of unsaturated systems by taking profit of formaldehyde-endowed two functions.

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ChemInform Abstract: New Three-Component Glyoxylation-Decarbonylative Stille Coupling Sequence to Acyl Heterocycles under Mild Conditions.

ChemInform ◽

10.1002/chin.201045112 ◽

2010 ◽

Vol 41 (45) ◽

pp. no-no

Author(s):

Boris O. A. Tasch ◽

Eugen Merkul ◽

Walter Frank ◽

Thomas J. J. Mueller

Keyword(s):

Stille Coupling ◽

Mild Conditions ◽

Coupling Sequence

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New Three-Component Glyoxylation-Decarbonylative Stille Coupling Sequence to Acyl Heterocycles under Mild Conditions

Synthesis ◽

10.1055/s-0029-1218802 ◽

2010 ◽

Vol 2010 (13) ◽

pp. 2139-2146 ◽

Cited By ~ 4

Author(s):

Thomas Müller ◽

Boris Tasch ◽

Eugen Merkul ◽

Walter Frank

Keyword(s):

Stille Coupling ◽

Mild Conditions ◽

Coupling Sequence

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The Diorgano Dichalcogenides Addition to Benzyne under Mild Conditions

10.3390/ecsoc-11-01344 ◽

2007 ◽

Author(s):

Fabiano Toledo ◽

Henrique Marques ◽

João Comasseto ◽

Cristiano Raminelli

Keyword(s):

Mild Conditions

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Pt-Pd Nanoalloy for the Unprecedented Activation of Carbon-Fluorine Bond at Low Temperature

10.26434/chemrxiv.11145098 ◽

2019 ◽

Author(s):

Raghu Nath Dhital ◽

keigo nomura ◽

Yoshinori Sato ◽

Setsiri Haesuwannakij ◽

Masahiro Ehara ◽

...

Keyword(s):

Activation Energy ◽

Low Temperature ◽

Dft Calculations ◽

Bond Activation ◽

Mild Conditions ◽

Selective Transformation ◽

Rate Determining Step ◽

Highly Active ◽

Harsh Conditions ◽

Reaction Profile

Carbon-Fluorine (C-F) bonds are considered the most inert organic functionality and their selective transformation under mild conditions remains challenging. Herein, we report a highly active Pt-Pd nanoalloy as a robust catalyst for the transformation of C-F bonds into C-H bonds at low temperature, a reaction that often required harsh conditions. The alloying of Pt with Pd is crucial to activate C-F bond. The reaction profile kinetics revealed that the major source of hydrogen in the defluorinated product is the alcoholic proton of 2-propanol, and the rate-determining step is the reduction of the metal upon transfer of the beta-H from 2-propanol. DFT calculations elucidated that the key step is the selective oxidative addition of the O-H bond of 2-propanol to a Pd center prior to C-F bond activation at a Pt site, which crucially reduces the activation energy of the C-F bond. Therefore, both Pt and Pd work independently but synergistically to promote the overall reaction

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Double Ring-Closing Approach for the Synthesis of 2,3,6,7-Substituted Anthracene Derivatives

10.26434/chemrxiv.12052647.v1 ◽

2020 ◽

Cited By ~ 1

Author(s):

Birgit Meindl ◽

Katharina Pfennigbauer ◽

Berthold Stöger ◽

Martin Heeney ◽

Florian Glöcklhofer

Keyword(s):

Wittig Reaction ◽

Condensation Reaction ◽

Synthetic Methods ◽

Anthracene Derivative ◽

Double Ring ◽

Mild Conditions ◽

Wide Range ◽

Anthracene Derivatives

Anthracene derivatives have been used for a wide range of applications and many different synthetic methods for their preparation have been developed. However, despite continued synthetic efforts, introducing substituents in some positions has remained difficult. Here we present a method for the synthesis of 2,3,6,7-substituted anthracene derivatives, one of the most challenging anthracene substitution patterns to obtain. The method is exemplified by the preparation of 2,3,6,7-anthracenetetracarbonitrile and employs a newly developed, stable protected 1,2,4,5-benzenetetracarbaldehyde as the precursor. The precursor can be obtained in two scalable synthetic steps from 2,5-dibromoterephthalaldehyde and is converted into the anthracene derivative by a double intermolecular Wittig reaction under very mild conditions followed by a deprotection and intramolecular double ring-closing condensation reaction. Further modification of the precursor is expected to enable the introduction of additional substituents in other positions and may even enable the synthesis of fully substituted anthracene derivatives by the presented approach.

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SuFEx Activation with Ca(NTf2)2: A Unified Strategy to Access Sulfamides, Sulfamates and Sulfonamides from S(VI) Fluorides

10.26434/chemrxiv.12026811.v1 ◽

2020 ◽

Author(s):

Subham Mahapatra ◽

Cristian P. Woroch ◽

Todd W. Butler ◽

Sabrina N. Carneiro ◽

Sabrina C. Kwan ◽

...

Keyword(s):

Room Temperature ◽

Medicinal Chemistry ◽

Mild Conditions ◽

Broad Array

A method to activate sulfamoyl fluorides, fluorosulfates, and sulfonyl fluorides with calcium triflimide, and DABCO for SuFEx with amines is described. The reaction was applied to a diverse set of sulfamides, sulfamates, and sulfonamides at room temperature under mild conditions. Additionally, we highlight the application of this transformation to parallel medicinal chemistry to generate a broad array of nitrogen-based S(VI) compounds.

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SuFEx Activation with Ca(NTf2)2: A Unified Strategy to Access Sulfamides, Sulfamates and Sulfonamides from S(VI) Fluorides

10.26434/chemrxiv.12026811 ◽

2020 ◽

Author(s):

Subham Mahapatra ◽

Cristian P. Woroch ◽

Todd W. Butler ◽

Sabrina N. Carneiro ◽

Sabrina C. Kwan ◽

...

Keyword(s):

Room Temperature ◽

Medicinal Chemistry ◽

Mild Conditions ◽

Broad Array

A method to activate sulfamoyl fluorides, fluorosulfates, and sulfonyl fluorides with calcium triflimide, and DABCO for SuFEx with amines is described. The reaction was applied to a diverse set of sulfamides, sulfamates, and sulfonamides at room temperature under mild conditions. Additionally, we highlight the application of this transformation to parallel medicinal chemistry to generate a broad array of nitrogen-based S(VI) compounds.

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Microwave-Assisted Decarbonylation of Biomass-Derived Aldehydes Using Pd-Doped Hydrotalcites

10.26434/chemrxiv.8069042.v1 ◽

2019 ◽

Author(s):

Nan An ◽

Diana Ainembabazi ◽

Kavya Samudrala ◽

Christopher Reid ◽

Kare Wilson ◽

...

Keyword(s):

Heterogeneous Catalysts ◽

Reaction Times ◽

Inverse Correlation ◽

Mulliken Charge ◽

Metal Leaching ◽

Carbonyl Carbon ◽

Mild Conditions ◽

Microwave Assisted ◽

Biomass Processing ◽

Alcohol Dehydrogenation

Here we report the synthesis, characterization and activity of tunable Pd-doped hydrotalcites (Pd-HTs) for the decarbonylation of furfural, hydroxymethylfurfural (HMF), aromatic and aliphatic aldehydes under microwave conditions. The decarbonylation activity reported is a notable improvement over prior heterogeneous catalysts for this process. Furfural decarbonylation is optimized in a benign solvent compatible with biomass processing - ethanol, under relatively mild conditions and short reaction times. HMF selectively affords excellent yields of furfuryl alcohol with no humin formation, but longer reaction can also afford furan via tandem alcohol dehydrogenation and decarbonylation. Yields of substituted benzaldehydes are related to calculated Mulliken charge of the carbonyl carbon. The activity and selectivity differences can be traced to loading-dependent differences in Pd speciation on the catalysts. Poisoning studies show inverse correlation between Pd loading and metal leaching: Pd-HTs with lowest Pd loading, which consist of highly dispersed and oxidized Pd species, operate heterogeneously with negligible metal leaching. Recycling experiments are consistent with this trend, offering potential for further optimization to improve robustness.

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Electron Donation by Low-Crystalline Ba-La-Ce Oxygen-Deficient Composite Oxide Accumulating on Ru Nanoparticles for Ammonia Synthesis under Mild Conditions

10.26434/chemrxiv.7763657.v1 ◽

2019 ◽

Author(s):

Katsutoshi Sato ◽

Shin-ichiro Miyahara ◽

Yuta Ogura ◽

Kotoko Tsujimaru ◽

Yuichiro Wada ◽

...

Keyword(s):

Ammonia Synthesis ◽

Bond Cleavage ◽

Synthesis Process ◽

Strong Electron ◽

Mild Conditions ◽

Ru Nanoparticles ◽

Rate Determining Step ◽

Highly Active ◽

Composite Oxides ◽

Low Crystalline

To mitigate global problems related to energy and global warming, it is helpful to develop an ammonia synthesis process using catalysts that are highly active under mild conditions. Here we show that the ammonia synthesis activity of Ru/Ba/LaCeOx pre-reduced at 700 °C is the highest reported among oxide-supported Ru catalysts. Our results indicate that low crystalline oxygen-deficient composite oxides, which include Ba2+, Ce3+ and La3+, with strong electron-donating ability, accumulate on Ru particles and thus promote N≡N bond cleavage, which is the rate determining step for ammonia synthesis.

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